Protein-containing textiles and stabilization thereof



United States Patent cc .v

PROTEIN-CONTAINING TEXTILES AND STABILIZATION THEREOF Melvin D. Hurwitz, Huntingdon Valley, and Benjamin B. Kine and Nathaniel A. Matlin, Levittown, Pa., assignors to Rohm & Haas Company, Philadelphia, Pa., a corporation of Delaware N0 Drawing. Application March 10, 1955, Serial No. 493,546

20 Claims. (Cl. 260-29.6)

shrink or render them substantially shrink-proof. An-- other object is to provide a process for shrink-proofing and felt-proofing textiles containing scale-surfaced protein fibers, whether of natural or artificial origin, through the use of the aforesaid dispersions. It is an object to 2,780,603 Patented Feb. 5, 1957" recommended, such as those containing isocyanate shrink-proof and felt-proof the textiles without adversely 1 affecting such other properties of the textile as wearing qualities, tensile strength, or hand. Still another object is to produce protein-containing textile materials, particularly woolen fabrics, which have a much reduced tendency to shrink and which also retain the desirable characteristics which are associated with woolen fabrics.

While this invention is principally concerned with improvemcnts of, .and more particularly the reduction ,of shrinkage and/or complete stabilization of, textile ma,- terials of proteinaceous types, and while the invention is described primarily in terms of wool-containing textiles,

proteinaceous fiber or a mixture of such fibers with other natural or synthetic fibers such as of cotton, linen, rayon, nylon, or polymers of acrylonitrile.

A number of different methods have been proposed for the treatment of textile materials formed of or containing wool or otherprotein fibers in order to pre-.-

vent or decrease felting and shrinking. In many cases such reduction in felting andshrinking tendencies has been obtained at the sacrifice of some other desirable property of the material. Some treatments damage the fiber and reduce the wearing qualities while others impart an undesirable harshness to the fabric. Other treatments are not permanently effective and may even cause an ultimate increase in shrinkage. Still other shrink-proofing methods are diflicult to apply with-uniformity and, create hazards to the workers involved in their applications.

Certain polymers of the linear type have also been groups and certain esters of acrylic or methacrylic acid, such as the glycidyl esters thereof. The types of polymers of this class that have been found effective for reducing the shrinkage and felting of protein-containing textiles have so far been of rather limited scope. It has been found that many polymers of this type, which are quite similar to those which are effective have no effect or have so little effect as to be of no practical value. For example, polymers or copolymers of glyceryl methacrylate, CH2=C(CH3)COOCH2CH(OH)CH2OH, are of this character.

The process of treating the textile materials in accordance with the invention comprises impregating them with an aqueous dispersion of the kind described in detail below and then heating the textiles at a temperature which is at least as high as 212' F., but which is lower than the charring point of the textile. During the treatment of the textiles in this way a chemical reaction is believed to take place between the proteinaceous portion of the textile and the copolymer in the dispersion. The copolymer appears to be chemically bound to the textile and not merely deposited as a dry coating on the fibers. As a result, the resinous copolymer is not leached or removed from the textile during subsequent wet-washing or dry-cleaning operations.

In accordance with the present invention, it has been 1 polymer of monoethylenically unsaturated molecules comprising at least 3% by weight of a chlorine-containing monomeric compound having the structure of the following general Formula I:

I CH2=CRCOOCH2CH( OH) CH2Cl -3-chloro-2-hydroxypropyl acrylate and 3-chloro-2-hydroxypropyl methacrylate. Homopolmers of these compounds can be applied to the fabrics for accomplishing the purpose of the invention. Frequently, however, it is preferable from the cost standpoint, and for controlling properties, such as hand, to copolymerize one of these monomers with 50% or more of one or more cheaper and more readily available comonomers. Preferred compositions of the invention are, therefore, those copolymers of from 3% to 30% of the chlorine-containing monomer or of a mixture of such monomers, the balance of the copolymer being formed of other less expensive comonomers.

Other polymerizable compounds containing a single ethylenically unsaturated group that may be copolymerized with the chlorine-containing monomer to produce binary, ternary, etc. copolymers include the esters of acrylic acid or' methacrylic acid with monohydric alcohols such as methyl, ethyl, butyl, octyl, dodecyl, cyclohexyl, cyanoethyl, benzyl, phenylethyl, and the like; diesters of itaconic acid and the above alcohols; esters of maleic, fumaric, or citraconic acids with the above alcohols; vinyl esters of carboxylic acids such as acetic, propionic, butyric, and the like; vinyloxyalkyl esters such as vinyloxyethyl acetate, etc.; vinyl ethers such as ethyl vinyl ether, butyl vinyl ether, octyl vinyl ether; methacrylonitrile or acrylonitrile; .acrylamide, or methacrylamide, and N-alkylsubstituted amides of thesetypes; vinyl toluene, vinylchloride, vinyl bromide, vinylidene chloride, vinylidene fluoride, vinylidene cyanide, 1-chloro-l-fluoroethylene, ethylene, and styrene.

The emulsifiers or dispersing agents that may be used for preparing the monomeric" emulsions before copolymerizationor dispersions of thepolymer after polymerization are preferably of the non-ionic type and include the following: alkylphenoxypolyethoxyethanols having alkyl groups of about seven to eighteen carbon atoms and 6- to 60. or more oxyethylene units, such as heptylphenoxypolyethoxyethanols, octylphenoxypolycthoxy ethanols, methyloctylphenoxypolyethoxyethanols, nonylphenoxypolyethoxyethanols, dodecylphenoxypolyethoxyethanols,v and. the like; polyethoxyethanol derivatives of methylene linked alkyl phenols; sulfur-containing agents such as those made by condensing 6 to 60 or more moles of ethylene oxide with. nonyl, dodecyl, tetradecyl, t-dodecyl, and the like mercaptans or with alkylthiophenols having alkyl groups of six to fifteen carbon atoms; ethylene oxide derivatives of long'chained carboxylic acids, such as lauric, myristic, palymitic, oleic, and the like or mixtures of acids such as found in. tall oil containing 6 to 60 oxyethylene units per molecule; analogous ethylene oxide condensates of long-chained alcohols, such as octyl, decyl, lauryl, or cetyl alcohols, ethylene oxide derivatives of etherified or esterified polyhydroxy compounds having a hydrophobic hydrocarbon chain, such as sorbitan monostearate containing 6 to 60 oxyethylene units, etc.; also ethylene oxide condensates of long-chain or branchedchain amines, such as dodecylamine, hexadecylamine, and octadecylamine, containing 6 to 60 oxyethylene groups; block copolymers of ethylene oxide and propylene oxide comprising a hydrophobic propylene oxide section combined with one or more hydrophilic ethylene oxide sections.

Particularly valuable resin dispersions are obtained by emulsifying a mixture of (a) one or more of the chlorine-containing monomers above and (b) one or more monomeric esters of acrylic, methacrylic, or itaconic acid or mixtures of these acids in Water and 01 merizin the P Y a mixture while it isin the emulsified form. The monomeric'csters which have proven to be most satisfactory are the alkyl esters in which the alkyl group contains one to eight carbon atoms and which are exemplified by the following: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, isoamyl, tert-arnyl, hexyl,

heptyl, n-cctyl, and Z-ethylhexyl acrylates, methacrylate's,

and itaconates.

The polymerizable emulsions can be prepared at temperatures from C. to about 100 C., but intermediate temperatures are much preferred. Thus, when the preferred copolymers with esters are made. with the esters in which the alkyl group contains one to four carbon atoms, a temperature from about C. to about 60 C. is employed whereas av higher temperature; e. g., 30 C. to 80 C, is recommended when esters containing five to eight carbon atoms in the alkyl group are copolymcrized. Peroxidic free-radical catalysts, particularly catalytic systems of. the redox type, are recommended. Such systems, as is well known, are combinations-of oxidizing agents and reducing agents such as a combination of potassium persulfate and sodium metabisulfite. Other suitable peroxidic agents include the .per-salts such as the alkali metal and ammonium persulfates andperborates, hydrogen peroxide, organic hydroperoxides such as tert-but'yl hydroperoxide and cumene hydroperoxide, and esters such as tert-butyl perbenzoate. Other reducing agents include water-soluble thiosulfates, hydrosulfites, tertiary amines, such as triethanolamine, and the salts, such as the. sulfates, of metals which are capable of existing in more than. one valence state such as cobalt, iron, nickel, and copper. The most convenient method of preparing the dispersions. of copolymcrs comprises-agitatingv an aqueous; suspension, or emulsion of a. mixture of copolymerizable monomers. and a redox; catalytic combination at room temperature without the application of external heat. The amount of catalyst can vary bu for purposes of efficiency from 0.01% to 3.0%, based on the weight of the monomers, of the peroxidic agent and the same or lower proportions of the reducing agent are recommended. In this way, it is possible to prepare dispersions which contain as little as 1% and as much as 60% or even more of the resinous copolymer on a weight basis. It is, however, more practical, and hence preferred, to produce dispersions which contain about 30% to 50% resin-solids.

The proportion of the polymer that is applied to the fabric may vary widely, such as from 1% to by weight of the fabric, a proportion of 3% to 10% being preferred. The hand or feel. of the fabric may be varied widely depending on the polymer selected. Thus, the chlorine-containing polymers which contain, in the place of R in the formula above, a hydrogen atom will generally have a softer hand than those with a-methyl group in place of R. The variation in hand may be controlled by the selection of the comonomer as well. Thus. with a given chlorine-containing monomer, a softer and more lubricous hand may be imparted by copolymerizing with a comonomer of such character that it introduces a longchain fatty group into the copolymcr. For example, the chlorine-containing monomer may be copolymerized with acrylic, methacrylic, or itaconic esters of alcohols containing from 1 to 18 carbon atoms, the longer the chain of the alcohol, the more lubricous the hand.

The dispersion is deposited on the textile material by such means as exhausting, spraying, or dipping. The textile material should be saturated and impregnated by the dispersion. This can be done at any desired temperature short of the boiling point of the dispersion. Ordinarily the textile is padded at room temperature with a dispersion which has been adjusted to a resin-content of about 1% to The material being treated must pick up or take up and'then' retain sufficient dispersion to provide from 1% to about 20%, and preferably from 3% to 10% of the copolymer, based on the weight of the dry textile.

The impregnated textile material must then be heated at a temperature between 212 F. and 400 F. for a period of about one-half minute to minutes, the higher the temperature, the shorter the period. required. A flash cure at-temperatures above 400 F. even up to 700 F. for short-periods of five to ten seconds may be employed In any event, the time and temperature should not be such as to damage the fabric. Preferably this heating is effected at a temperature from 240 F. (for about 10 to 15 minutes) to about 310 F. (for about 5' to 10 minutes), and it is believed that it effects some chemical reaction involving the polymer and possibly the textile. In any event, the heating sets the polymer on the textile, and in the case of wool, reduces shrinkage and/or imparts full dimensional stability thereto. Drying of the treated'textile and the heat-treatment which effects the'chemical reaction can be carried out simultaneously or concurrently in one step, or the textile can be substantially or completely dried at a conveniently lower temperature and then heated later at the higher temperature. As will be evident to those skilled in the art, theoptimal length of the heating period depends on the particular temperature which is employed, on the particular'copolymer, and on the quantity thereof which is on the: textile. But in any case the heat-treatment does not require along period and is usually measured in minutes, generally one to thirty minutes and preferably about five to fifteen minutes. The most satisfactory time of heating for any particular combination of dispersions and textile isreadily determined by heating pieces of the impregnated textile for varying lengths of timeat a given temperatu'reand then measuring the; resultant stabilization of the individual pieces by' means ofawe't-washi'ngtest.

The aqueous dispersions of the homopolymers of the chlorine-containing monomers of Formula I and many of their copolymers especially those with alkyl acrylates or methacrylates mentioned above, are generally colorless, non-toxic, non-irritating, and free of anydisagreeable odor, before, during and after application to the fabric. They are easily applied, involve no fire hazard, and require no solvent recovery system. They do not alter the color of the wool, whether dyed or not. The finished fabrics are generally not deleteriously altered, and are frequently improved, in respect to their resistance to deterioration on exposure to sunlight, heat, and normal ageing conditions.

In some cases, it may be advantageous to add an acid or acidic substance to the dispersion with which the textile is treated to accelerate the reaction and to bring about the stabilization or reduction in shrinkage in a shorter period of time at a given temperature or at a lower temperature in a given time. Strong acids such as formic, oxalic, sulfuric, and phosphoric acids are recommended. There may also be used acidic substances or salts that are substantially neutral at ordinary temperature but liberate acid on heating duringthe curing stage, such as ammonium phosphate, ammonium thiocyanate, hydrochloric or other acid salts of a hydroxy aliphatic amine including 2 methyl 2 amino l-propanol, 2-methy1-2- amino 1,3-propandiol, tris(hydroxymethyl)aminomethane, 2-phenyl-2-amino-l-propanol, Z-methyI-Z-amino-lpentanol, Z-aminobutanol, triethanolamine, 2-amino-2- ethyl-l-butanol, alsoammonium chloride, pyridine hydrochloride, benzyldimethylamine oxalate. For this purpose from 1% to 2% acid or acidic substance, basedon the weight of the pad liquor, is suggested. The textiletreating dispersion of the present invention may contain a polyamine, such as ethylenediamine, diethylenetriamine, and triethylenetetramine, and such polyamine may be used with or without an acidic catalyst of the type just mentioned. The polyamine may be regarded as an auxiliary reactive substance which apparently crosslinks the chlorine-containing polymer, and may be used in an amountof 1% to 5% on the weight of the copolymer in the dispersion.

It has also been found that the use in conjunction with the dispersions of such acid catalyst with other auxiliary reactive substances, such as formaldehyde, or materials which are equivalents of formaldehyde, such as glyoxal or formals, or mixtures of formaldehyde or the like with aminoplast-forming compounds, or weight, water-soluble, reaction products, preferably of formaldehyde or the like with such compoundaenhances the stabilization of. woolen or proteinaceous textiles. While such auxiliary reactive substances and .the acid catalyst may be employed as an added component of the dispersions, they may also be employed by applyinga solution of the auxiliary reactive substance and the acid catalyst after the textile has been treated with the dispersion. The use of the auxiliary reactive substance is advantageous in some cases where it becomes especially evident on extended laundering of the textile. Also in. combination fabrics, such as those containing fibers or yarns of silk or cellulosic type, such as cotton or rayon, as well as fibers or yarns of proteinaceous types, such as wool, including as an example woolen garments sewn together with cotton threads, the use of the a'uxiliaryreactive substance serves to reduce shrinkage of, or com-' pletely stabilize the first-mentioned fabric components while the linear polymerdispersion acts similarly upon the proteinaceous or woolen components.

Examples of the aminoplast-forming compounds include urea, thiourea, biuret, or other homologs .or derivatives thereof, such as N,N-ethyleneurea, N,N'-ethyleneurea, N,N'-dimeth'ylurea, N,N'-diethylurea, N,N-dimethoxymethylurea, N.N-dimethoxymethylurea,' N,N'-. diethoxyethylurea, tetramethoxymethylurea, tetraethoxy-i ethylurea. Similar reaction products of formaldehyde low-molecular 'tion of the resin content and 1% of sulfuric acid was added and applied to a wool flannel as described above. 1 I

with triazines, such as melamine, N,N-dimethylmelamine, etc. and alcohol-modified melamine-formaldehyde thermosetting resin condensates, e. g., of methyl and ethyl alcohols, for example, dimethoxymethyl-monomethylolmelamine may also be employed.

The treated textiles are characterized by greater resistance to abrasion and/or reduced shrinkage and, in many cases, fully practical dimensional stability against laundering, by which is meant that they are substantially shrink-proof. They do not stiffen, degrade or discolor on aging or on exposure to ultraviolet light as do comparable textiles which have been treated, for example, with latices of butadiene copolymers.

The effectiveness of the dispersions exemplified below in stabilizing wool was determined by impregnating measured pieces of flannel with them, drying, and heating the impregnated pieces of flannel at a temperature of 240 F. or higher, laundering the pieces in hot water, th'en drying them and measuring the shrinkage. In these tests, piecesof woolen flannel, 2/2 right hand 45 twill, 55 x 44; S-twist in ends, Z in picks, were used. All pieces were 10 inches square, with axes along the yarn systems. The pieces of flannel were padded with a pad liquor of the resin dispersion which was so adjusted in solids-content as to provide the desired amount of resinssolids (1% to 20% based on the weight of the dry flannel) at a pick-up of about 75%; that is, when the flannel contained the emulsion in an amount equal to about 75% of the weight of the dry flannel. The treated specimens were dried and heated and cured 'at a temperature of at least 240 F. The specimens were washed, together with untreated pieces of flannel, in a Cascade wheel washer containing 70 grams of soap (Ivory) in 10 gallons of water for five hours. In all cases the load in the washer was made up to three pounds with cotton t-ow'eling and the temperature was maintained at 140 F. The values of shrinkage are given as percentage reduction in the initial area after taking into account any inherent residual shrinkage in the initial fabric that may be present as a result of previous drying under tension, and is removable by simply wetting and drying. In other words, the shrinkage values hereinbelow are obtained by subtracting relaxation shrinkage from the actual shrinkage measured.

The following examples serve to illustrate this invention:

Example 1 A dispersion of a copolymer was prepared by emulsifying parts by weight of n-butyl acrylate with 20 parts by weight of 3-chloro-2-hydroxypropyl methacrylate in about 300 parts by weight of water with about 6 parts by weight of an ethylene oxide condensation product of an octyl phenol containing between 30 and 50 oxyethylene units per molecule. To the emulsified monomers 0.3% by weight of ammonium persulfate, 0.06% of sodium hydrosulfite, and 1% triethanolamine were added to catalyze the copolymerization which was carried out for a period of about fifteen minutesduring which the temperature rose from 20 C. to 45 C.

The resin dispersion was diluted to a 5% concentra- After drying 10 minutes at 240 F., followed by curing for 10 minutes at 300 F., itwas found that the proportion of copolymer applied to the fabric was about 3 /z% of the weight of the fabric. The shrinkage of the treated fabric after the five-hour wash described hereinabove was 3%. The untreated control shrank 36% after such av wash.

I Example 2 V v The procedure of Example 1 was followed except that the resin dispersion is diluted to 6% to 7% concentration (instead of 5%) and then applied to the wool. After drying and curing, it was determined that 5% by weight 'of the copolymer had been applied to the fabric. The shrinkage of the treated fabric after the five-hour wash was 1% while the untreated control shrank 33% after such wash.

Example 3 The procedure of Example 2 was followed except that after drying the fabric at 240 F., it was passed through a 1% solution of formaldehyde and then dried 10 minutes at 240 C. and cured for a period of 10 minute sfat 300 F. The resultingfabric showed no shrinkage after the five-hour wash test. Whereas the hand obtained in Example 2 was softer than that of the initial fabric, the formaldehyde treatment reduced the softness of the hand only slightly as compared to the product of Example 2.

Example 4 Asimilar dispersion was prepared of a copolymer of 95 parts by weight of -n-butyl acrylate with 5 parts by weight of 3-chloro 2r-hydroxypropyl acrylate. The procedure of Example VI was followed and the shrinkage after a five-hour wash was found to be 5% as compared to a 36% shrinkage of a control fabric after only two hours washing with other conditions remaining the same.

Example 5 The procedure of Example 2 was followed with an aqueous dispersion of a copolymer of 80% 2-ethylhexyl acrylate with 20% of 3-chloro-2-hydroxypropyl methacrylate. The treated fabric exhibited '8% shrinkage after the five-hour was'h as compared with a-41% shrinkage of the control and had an extremely soft handboth before and after the wash.

Example 6 The procedure of Example '3 was followed with the copolymer of Example 5. The formaldehyde treatmentaltered the hand only slightlyand the shrinking was reduced to 1% after the five-hour wash. 7

Example 7 The procedure of Example 1 was followed with an aqueous dispersion of a copolymer of 85% s-butyl acrylate with 15% of 3-chloro-2-hydroxypropyl acrylate. After the five-hour wash test, the fabric exhibited only 4% shrinkage.

Example 8 The procedure of Example 1 was followed except that after drying the fabric at 240 B, it was passed through a 3% aqueous solution of dimethoxy'methylur'ea and cured for a period of 10 minutes at 300F. The fabric showed no shrinkage as a result of the five-hour wash test.

Example 9 ing textile materials comprising an aqueous dispersion of a water-insolublelinear polymer exclusively of monoethylenically unsaturated molecules comprising at least 3% by weight of a monomer having the formula where R is selected from the group consisting of hydrogen and methyl.

2. A composition for the treatment of protein-scontaining textile materials comprising an aqueous dispersion ofva water-insoluble linear addition polymer exclu'sively' of =inonoethylenically unsaturated molecules comprisingzat leastr3% by weight of 3-chloro-2 hydroxypropyl :acryla't'e.

39A composition 'for the treatmentof protein-containing textile :mat'erials comprising an aqueous dispersion of a water-insoluble linear addition polymer exclusively of 'monoethylenically unsaturated molecules comprising at least 3% by weight .of 3-chloro-2-hydroxypropyl metliacrylate.

"4. As an article of manufacture, 'a textile material comprising :protein fibers carrying from 1% to 20% of a water-insoluble linear addition polymer .as defined in claim 1.

5. .As an article of manufacture, a textile material comprising proteinlfibers carrying from 1% to 20% of a water-irisoluble linear addition polymer exclusively of monoethylenically unsaturated molecules comprising at leastl3% of 3-chloro-2-hydroxypropyl acrylate.

6..As an article of manufacture, a textile material comprising ,protein zfibe'rs carryingfrorn 1% to 20% of a water-insoluble linear addition polymer exclusively of monoethylenically unsaturated molecules comprising at least 3% of v3-chloro-Z-hydrhxypropyl methacrylate.

-7.:As an article of vmanufacture, a textile material comprising,proteinrfibers'carrying from 1% to 20% of a waterdnsoluble linear addition copolymer exclusively of monoethylenicallyunsaturated molecules comprising 3% to 301% of ('=lt) amondmer having the vformula defined in claim land (2) at least one ester of an acid selected from the group consisting of acrylic, methacrylic, and itaconiczacids with analco'hol having an alkyl group of l te 18 carbon atoms.

8. As an article of .manufacture, a textile material comprising wool "fibers carrying from 1% to 20% of a water-insoluble linear addition polymer exclusively of monoethylenically unsaturated molecules comprising at least 3 of S-chlo'roQ-hydroxypropyl 'acrylate.

-9 .-As an article of manufacture, a textile material comprising wool fibers carrying from 1% to 20% of a water-insoluble linear addition polymer exclusively of monoethylenically unsaturated molecules comprising at least 3% of 3-chloro-2-hydroxypropyl methacrylate.

10. ;As an article of manufacture, a textile material comprising wool fibers carrying from 1% to 20% of a pol-ymerof -80% of n-butyl acrylate and 20% of 3- chloro-Z-hydroxyprqpyl methacrylate.

11..As an article of manufacture, a textile material comprising wool fibers carrying from 1% -to 20% of a polymer;of -.80% of -n-butyl acrylate and 20% of 3- chlord-Z-hydrdxypropyl acrylate.

12. As an-articleof manufacture, a textile material comprising protein-fibers carrying from 1% to 20% of apolymer-of 80% of n-butyl acrylateand 20% of 3- chloro-Z-hydroxypropyl methacrylate.

13. A process for treating proteinaceous textile materials to reduce the shrinkage thereof comprising treating-such a material with an aqueous .dispersion of a water-insoluble linear addition polymer exclusively of monoethylenically (unsaturated molecules comprising at least 3% by weight, inthe polymer molecule, of a monomer having the formula where k ts-selected from the group consisting of :hydrogensarrd methyl; v

.14. Thefprocess of claiin l3 *in' whi'ch the polymer-is a :copolymer of 3-chloror2=hydroxypropyl acrylate with butyl acrylate. I 1

1S..Theiprocesstof"claim 13in which tliepolymeris a "copolymer of i3=chloro-2ahydroxypropyl' methacrylate with butyl acrylate.

16.'The process :of claim 13 in which'the polymerris a copolymer of 80% of n-butyl .acrylate and 20% of 3=chloro-2+hydroxypropyl -methacrylate.

.17. 'The process of claim 13 in which the polymer is in. a.

ethylenically unsaturated molecules comprising 3% to 30% by weight of (1) a monomer having the formula where R is selected from the group consisting of hydrogen and methyl and (2) at least one ester of an acid selected from the group consisting of acrylic, methacrylic, and itaconic acids with an alcohol having an alkyl group of 1 to 18 carbon atoms.

No references cited. 

1. A COMPOSITION FOR THE TREATMENT OF PROTEIN-CONTAINING TEXTILE MATERIALS COMPRISING AN AQUEOUS DISPERSION OF A WATER-INSOLUBLE LINEAR POLYMER EXCLUSIVELT OF MONOETHYLENICALLY UNSATURATED MOLECULES COMPRISING AT LEAST 3% BY WEIGHT OF A MONOMER HAVING THE FORMULAR
 7. AS AN ARTICLE OF MANUFACTURE, A TEXTILE MATERIAL COMPRISING PROTEIN FIBERS CARRYING FROM 1% TO 20% OF A WATER-INSOLUBLE LINEAR ADDITION COPOLYMER EXCLUSIVELY OF MONOETHYLENICALLY UNSATURATED MOLECULES COMPRISING 3% TO 30% OF (1) A MONOMER HAVING THE FORMULA DEFINED IN CLAIM 1 AND (2) AT LEAST ONE ESTER OF AN ACID SELECTED FROM THE GROUP CONSISTING OF ACRYLIC, METHACRYLIC, AND ITACONIC ACIDS WITH AB ALCOHOL HAVING AN ALKYL GROUP OF 1 TO 18 CARBON ATOMS. 